Process of making by-products from inactive and inert oils or gases



I Jan. 22,1929.

C. S. PALMER PROCESS OF MAKING Bil-PRODUCTS FROM INACTIVE AND INER'I' OILS DR GASES Slants-Shoot 1 /vvE/v-ro flrr'y.

Filed Sept. 28. 1921 Jan. 22, 1929. 1,699,627

Q s. PALMER rnncas OF MAKING BY-PRODUCTS Fnou INACTIVE AND INERT OILS OR GASES iiled Sept-28; 1921 3 Shuts-Shoot 2 flrry I I' I h m I H! II! Hll Jan. 22, 1929.

c. s. PALMER PROCESS OF MAKING BY-PRODUCTS FROM INACTIVE AND INBRT OILS 0R GASES I INVENTOR I ATTORNEY Patented Jan. 22,1929.

UNITED, STATES PATENT OFFICE.

CHARLES 8. PM, 0] PITTSBURGH, PENNSYLVANIA.

rnocnss or name nv-raonuc'rs anon INACTIVE AND man one on cases.

Application filed September 2 8 1921. Serial No. 503,901.

Most natural hydrocarbon oils and gases are inactive in their chemical nature so that they will not only pass through ordinary acids, alkalies and salts without reaction, but they will also stand a considerable degree of heat, even if mixed with some air or oxygen, without ignition or burning or ox1dation.

One of the exception to this, and frequently a point of attack, is the use of chlorine, or one of the other halogens is used for attacking of para-Hines, but owing to the high cost of chlo1'ine-as compared with the free oxygen of the atmosphere-and also the fact thatthe product obtained is frequently inactive, the chlorine method is frequently made impracticable.

In considering the problem of the oxidation of the parafiines it should be noted primarily that the general purpose is a. favorable one, because it is exothermic, that is, oxidation of the paraflines or related hydrocarbons means the giving off of a great amount of heat; and

this means that the general processes of oxidizing the parafiines may be compared in their relations to natural physical economies and possibilities to the rolling of rocks down hill,not up hill.

, To carry on this figure of rolling rocks down hill as an illustration in showing the obvious possibility of oxidizing the paraffines. after i the oxidation or burning is once started by the proper. ignition, one may say that the chemical .engineer is in the position of those at the top ofia precipice who would roll rocks down hill. But, note that these rocks must be rolled to the-edge of the precipice, and there is also a slight elevation, or ridge, or hump, overwhich they must be rolled. After they are once lifted over this ridge (which represents ignition) they will themselves roll down hill to the bottom. provided they are supplied with the requisite amount of oxygen for their complete combustion. But it is the trick, or the uniqueness of the-chemistry of the paratfines and their related hydrocarbons. that they frequently require special conditions and devices to be started over the hill edge hump on this down hill rolling of oxidation.

Much experience, observation and experimentation for many years has shown me that while the ordinary paraflines are quite inert, and their ignition is controlled with. difficuIty,-evcn under apparently favorable circumstances-yet, many related hydrocarbon compounds notably those 'of the various unsaturated series-lend themselves more easily to ignition, burning or oxidation. Now, thesefso-called unsaturated hydrocarbons,'which are more or less active chemically, can be obtained readily from the inactive parafline hydrocarbons, as by cracking; and this process of cracking the paraffines seems to be a promising preliminary treatment for changing the inactive parafline hydrocarbons into such active hydrocarbons as can be more readily ignited or oxidized.

Once having changed the inactive parafiine hydrocarbons and the less active unsaturated hydrocarbons into more active hydrocarbons, the next step is to mix them with theri ht quantity of air or oxygen for the desire degree of oxidation. This air or oxygen may, of course, be preheated to assist in the oxidation or burning.

The next step after changing the inactive or partially active hydrocarbons into more active hydrocarbons,as by cracking-is, of course, to start the oxidation ball rolling down hill, as by suitable ignition, and this oxidation or burning of the mixed active hydrocarbons and oxygen or air is carried on in a suitable igniter.

Having thus specified some of the objects and salient features of the present invention I will now proceed to descrlbe the same with reference to the accompanying-drawings illustrating several apparatus such as may be used for carrying out the invention, and in Which drawings Figs. 1 and 2 illustrate suitable apparatus, more or less diagrammatic; Fig. 2 being a continuation of Fig. 1 to showa complete ap-,

'paratus; and

metering, may be supplied in the first instance instead of oil. The oil reservoir 10 is provided with a discharge nozzle 12 controlled by regulating-valve 13, there being a I sightgauge 14 introduced between the nozzle -12 and a pipe 15. The oil maybe regulated preferably through the employment of suitable ca-talytics, as for example, the catalytic may be in the form of confined sheets 18 of Wire clotl1,-'asof Monel metal.

The catalyticemployed. in the cracking;

chamber is not necessarily limited to Monel metal, (which is illustrated). I have found that other metals, such as iron, nickel, copper, chromium or other alloys, or alloys of related elements may be used as catalytics and are Very eflicient in promoting cracking.

The cracking chamber 16 isv connected by a pipe 19 with a-mixing chamber 20, Which is provided with suitable interior perforated or reticulated elements orthe like 21, asmixing baffles, for the purpose of facilitating-admixture of oxygen, as,'for instance, that contained in the atmosphere with the vapors emanating from the cracking chamber 16. Air pipe 24 is connected with a coil 23 constitutin a preheater, supplied by means of an air compressor 25 at one end of pipe 24 between which compressor and the inlet end of coil 23 a suitable .meter 26 is arranged. The compressed air is'preheated in the coil 23 by reason of the fact that it is enclosedin a heating chamber 22, which likewise contains the cracking chamber 16 and the burner 17. One end of the preheating coil 23 is connected with the vapor inlet end of the'mixing'chamber 20, and. the

other end of the pipe '24 between the inlet end of the preheating coil ofthe oil reservoir '10 constitutes means for introducing air pressure over the body of oil in the reservoir 10 so as to prevent back pressure from-liftmg the oil'in' feeding.

chamber. from which the comming'led vaporized oil or thegas is conducted,togetherwith the admixed air, to an igniting chamber 29,

which preferably contains an; activating or catalytic filling 30, preferably of such materials as iron, copper, platinized, asbestos,

vanadium asbestos, etc, to to assist in ignition or oxidation, and at temperaturesprefen ably between 300? Centigrade as a lowerlimit, and 700 Centigrade asan upper-"limit- The igniting chamber3Q and its contents are kep't moderately hot by meansof a burner 31.

Heating means may be used as part of the apparatusand are here sho'wnas a chamber '32 provided with headers. 33, 34 for tubes 35 I which pass through the chamber 32, it being vpossible to use this heat control by employing the latent heat of the 'vaporizationof hot and such air may be to the header 34 and the mixed gases, etc. pass down through the tubes 35-to the header 33 l and out at a discharge pipe 37. An accessory circulating pump may be used. The heat control means are preferably regulated in any suitable way, as by means of a watercircuably controlled by means of hand-operated valves 41, 42. Steam may be led from the steam-space of. the chamber 32 by means of an outlet pipe 43-through a meter 45, andfrom thence throu h a pipe46 controlled by a valve 47 to the pipe 28 which connects the mixing chamber 20 with the igniter 29. Pipe 43 is preferably controlled by a valve 44 just ahead of the meter 45. A valved steam-pipe 43, may supply steam independently of, or

with, the heat-control means 32, etc.-

- It will be seen that so far as described the ignition i'n igniting chamber 29' of the ordinary paraflines, afterbei'ngcracked, is rendered favorable by such previ 'ous cracking, and that this applies not only to ordinary parafiines which are'quite inert, but'to many related hydrocarbon compounds, so that oxi-- dation by ignition in the igniter .29 is ren; dered possible. I

In the process of oxidizing the-cracked oils I action and presenceof steam a very smoky A pipe 28 connects that end of the mixing process herein described, on, the burning of cracked hydrocarbons in the ignitcr, would promote extreme oxidation (with a production of CO which here is not wanted, as it means rolling the rocks to the bottom of the hill and a waste both of chemical products and energy, in that the carbon compounds burn to CO but I found that the action of steam on the igniter, under the conditions of the apparatus and process used, was not to produce extreme oxidation, giving CO but a modified oxidation, producing the aldehydes, and possibly. some of,the aldehydefrom the steam.

alcohols or alcohols. Of course, it is obvious that this apparatus and process aims to produce materials and products of limited oXidation, not complete oxidation, (to CO and results involving unnecessary waste.

This action of steam also in this apparatus and process is useful not only in promoting and controlling the oxidation, but also in gatheringup the condensed aldehyde compounds,-and possibly, some related compounds--in the condensed water which comes Of course, there is some water produced inthe oxidation without the introduction of steam. Also, the range of plain saturated steam and superheated steam are different, and vary with the original oil or gas used, and also, with the degree and kind of cracking, not to ignore also the variation with the action of specific catalytics. I do not limit myself to any particular side of this.

InFig. 1 a partial supply of steam is obtained from the heat control means 82, etc., but it is obvious that the steam may be supplied from any suitable source.

Thermometric devices 48, 49, 50, 51, 52 and 53 are preferably employed for determining and regulating the more desirable temperatures at cracking chamber 16, hot air pipe 27, mixing chamber 20, igniting chamber 29, heat control means 32,'ete., and at pipe 37, respectively. These temperature regulators may be of any suitable or approved design.- They may also be introduced elsewhere, as needed.

Connected with the pipe 37 is a preliminary condenser 55, said pipe beingflcontrolled by valve 54. This preliminary condenser preferably discharges the condensed vapor and air mixture',all of which is not condensed at this pointinto a receiver 56, which is provided with taps 57, 58 for dis charging recovered oil and water, respectively, or other products, the oil, of course, being at the higher level in said receiver. From the preliminary condenser the remainingportions of the mixture are conducted through a condensing device, preferablysuch as shown, described and claimed in my copending applicatiom Serial No. 370,126, filed March'31, 1920. This second condenser comprises a zig-zag condensing tube 60 leading from the pipe 59 and surrounded by a coolingjacket 61 connected with water supply and discharge pipes 62, 63. The second condenser discharges by a pipe 64 into a second receiver 65 provided with taps 66, 67 for respectively discharging layers of recovered oil and water.

A branch pipe 7 O is shown as leading from v the pipe 64, ahead of the second receiver 65, and it may be controlled by a Valve 71. Pipe 70 leads to a condensing pump 7 2 for forcing the condensed vapors or gas-through a pipe 74, a cooling coil and a cooling device 7 3. From the coil 75 there leads a pipe 76 to a tion'of other materials.

which it connects at a point adjacent the pipe 68, said pipe 76 being controlled by a valve 78. The drawings show only a simple condenser, yet it is clear that the invention is not limited to the use of water in the cooling jacket at ordinary temperatures, but also cold solutions may be used; and of course, all the usual accessories of condensing devices may be used to assist in the condensation of any products produced. The more volatile gases and vapors, as, for instance, acetic and formic aldehyde would be condensed by the by-pass condensing system 70 to 76, especially in the troublesome condensation temperatures of warm weather.

From the second receiver 65 there leads a pipe 68 provided with a valve 69, and this pipe leads, through the leg 81, tothe fog and tar arrester 80. These last named parts are shown in Fig. 2, and the other parts therein shown will now be described. In passing, it is stated that good results in the fog arrester have been obtained by a filling of such material as wire cloth in strips, bundles and rolls, and other forms of metal, such as metal excelsior, and, indeed, common excelsior. It is clear that,.as the destruction and absorption of the tar, oil or gas fog is a surface matter, the fog arrester will work much better as soon as the surfaces therein become slightly saturated with the very materials they are absorbing. I do not limit myself to this, but use also such precipitation as the Cottrell, or

' the like.

From the fog arrester there leads a pipe 82 for carrying off the remaining vapors which may be condensed or treated for the produc This pipe 82 leads to an absorber 83. provided with an inner flanged spiral 84, and this absorber is preferably of the type shown, described and claimed in my co-pending application Serial No. 365,271, filed Ma rch 12, 1920. The said absorber is for the purpose of recovering the vapor of the aldehydes, at. least. From the absorber 83 there leads a pipe 85 to a second absorber 86 containing aflanged spiral 87, and arranged, constructed and operated preferably as disclosed by said application, Serial No. 365,271. In the second absorber sulphuric acid is preferably employed for use in the recovery of unsaturated hydrocarbon compounds leading to the alcohols. The sulphuric. acid absorber 86 is provided with a discharge pipe 88 for the remaining vapors, and this pipe discharges into a third absorber 89, preferably provided with a spiral 90 and, constructed in accordance with said application, Serial No. 365,271. In this absorber 89' specific compounds are recovered from the unknown gases group. Leading from the third absorber 89 is a pipe 91 of any desired length so as'to supply the remaining third receiver 76 for the condensate, and

tail gas at an adjacent point or some remote point. This tail gas is suitable for making good carbon black by suitable burning and collection, and to that end the pipe 9]. may be provided with burners 92 for depositing the carbon black upon collecting surfaces 93, from which the samema-y be removed and saved.

'Among the many curious aspects and phases of the many-sided reactions involved and implied in this apparatus and process,

one of the most interesting is thecurious trickery which mother nature uses and which must be anticipated and provided for. For instance, it frequently happens that using measured quantities of oil, for instance, at

the start, with a tight apparatus with no leaks, some of the products which must be produced seem almost at times to disappear before ones eyes. T hus, the aldehydes which are produced in considerable quantities are not all in the steam water or oxidation water in receivers 56 and 65, nor arethey all in the fog arr-esters or the water-absorption bottles, but they must be somewhere and it was found that the condensed recovered oil found in receivers 56 and and in the fog arresters was itself a rich solution or emulsion of absorbed aldehyde compounds. These absorbed aldehyde compounds can be shaken out from this oil by a generous quantum of water in which the aldehydes dissolve readily, This observation involves many new possibilities in the production and use of varnishes, paints, inks and the like.

In connection with the cracking step of the process herein described, at times more or less hydrogen seems to be produced; and some of this hydrogen may appear in the final tail gas. or it may be absorbed at certain places, as by adding itself to some of the unsaturated hydrocarbons; and this possibilityv must be considered in explaining the 0,, reaction, whereby-derivatives may be obtained not merely of unsaturated compounds, but of saturated compounds.

Also. in this connection'it should be noted that while we usually-consider-in a broad qualitative sense-that water is neither an oxidizer or reducer, but is a sort of.chemical bank of exchange, receiving and imparting both oxidizing and reducing actions; and, in-

asmueh as it is possible that water may add itself to the unsaturated hydrocarbons, such as ethylene C,H ,-producing ethyl hydroxide, C,H Oherein we have a curious case, where water is acting .as though it were an oxidizer,the real action, of course, involved must be referred to the nature and action of the unsaturated ethylene ;and this is an illustration of many other related cases, both known and unknown.

Regarding the use herein of the terms ignition, igniter, or the like, of course it is obvious that what is meant is not ignition I in theproper sense of burning with a visible flame, but rather, such a 'modified'hidden as will meet the demands implied in the apparatus, process a'iid results. Of course,

open visible ignition which is attended with visible flame, almost invariably means rather extreme oxidation with a production of CO and other waste products which are not primarily intended or desired.

It is obvious that there are two possibilities for the addition of water or steam to unsaturated molecules. One of these is where the steam is added directly to the unsaturated molecule shortly after cracking, and would result in a combined oxidation-reduction addition product which might change the unsaturated compound into a correspond ing saturated alcohol for instance, ethylene plus'water equals ethyl hydroxide.- Another kind of hydration may be illustrated in the subsequent treatment of the unsaturated hydrocarbons caught in thesulphuric acid absorber whereby ethyl sulphate is changed into sulphuric acid and alcohol.] And either or both of these reactions and results may occur in the same cycle, but in different parts of this apparatus and process.

Referring to Fig. 3, a modification is shown in'which the heat control means 32, etc, herein described are omitted. In this modification thessupply of the desirable steam to the vaporsor gas preliminary to ignition may be obtained from an independent source of steam, as through a pipe 94:, or through the medium of any suitable superheater, such as 95, for the purpose of supplying superheated steam. It will be noticed that in this modification the igniter 29 is connected directly with the preliminary condenser 55, as it may be found that in some cases proper regulation and control may be obtained without the introduction of heat controlmeans, such as 32,

etc. This is but one of the many possible modifications to which the present apparatus ingthe hydrocarbon constituents with such I preheated gas.

2. The continuous process of making byproducts from inactive and inert oil or gas,

which consists in cracking such oil or gas and thereby vaporizing and rendering the hydrocarbon constituents more active and capable of oxidation, mixing preheated oxygen with the vaporized hydrocarbons while they are still heated as a. result of the cracking, and then partially oxidizing the heatedvapors in a separate chamber.

3. The continuous processof making byproducts from inactive and inert oil or gas,

-which consists in cracking such oil or gas and thereby vaporlzing and rendering the hydrocarbon constituents more active and capable of oxidation, mingling steam with said constituent-s, partially igniting the constituents for the recovery of the by-products, and passing the partially oxidized products'in contact with heat-regulating surfaces cooled by a liquid, said steam being supplied by said 1iquid.-

4. The continuous process of making byproducts from inactive and inert oil or gas, which consists in cracking such oil or gas and thereby vaporizing and rendering the hydrocarbon constituents more active and capable of oxidation, igniting the constituents forthe 

